Pt-Al-Hf/Zr coating and method

ABSTRACT

A Pt—Al—Hf/Zr aluminide coating that can be used as a bond coat for TBC and improve TBC spallation life in service at elevated temperatures is provided. The aluminide coating can include a metastable ternary or higher X—Pt/Pd—Ni phase where the phase and other elements in the alloy system are present in a NiAl β phase of the coating. The metastable phase can be present and observable in the as-deposited condition of the bond coating; e.g. in an as-CVD deposited condition of the bond coating.

This application claims benefits and priority of U.S. provisional application Ser. No. 61/216,649 filed May 20, 2009, the entire disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to Pt—Al—Hf/Zr aluminide coatings for gas turbine engine blades and components and to a method of introducing alloying elements to a surface region of an alloy.

BACKGROUND OF THE INVENTION

Increased turbine engine performance has been achieved through the improvements to turbine alloys, cooling scheme, and coatings. The most improvement from coatings has been through the addition of thermal barrier coatings (TBC) to cooled turbine components. For turbine blades, the most effective TBC has been applied by Electron Beam Physical Vapor Deposition (PVD). Prior art includes NiCoCrAIY, aluminide and platinum-aluminide bond coats. Evolutionary improvements to these bond coats has been realized in terms of optimal processing to produce improved surface finish or clean processing to reduce the significant effect of contaminates such as S (sulfur). However, turbine designers are not making full use of TBCs because their predicted life does not meet the component design life at higher turbine temperature or TBC life at existing temperatures are not reliable. Consequently a need for more reliable and longer life TBCs exists.

Addition of Hf to alloys is relatively easy and has shown a significant impact on TBC spallation life when high Hf alloys [higher than single crystal alloys (SXL) specification or directional solidification (DS) alloys with high Hf for improved castability] are coated with current outward type Pt—Al aluminide bond coats. SXL alloys have shown 3× to 5× (3 times to 5 times) life improvement while DS MarM247 has been reported to have 10× life improvement relative to baseline SXL TBC life. For SXL, the high Hf additions impacted SXL alloy microstructure and mechanical properties negatively.

SUMMARY OF THE INVENTION

The present invention provides a Pt—Al—X aluminide coating (X is Hf and/or Zr) that can be used beneath a TBC and improve TBC spallation life in service at elevated temperatures. In an embodiment of the invention, the Pt—Al—X aluminide coating includes a metastable (transitional) X—Pt/Pd—Ni phase where X is Hf and/or Zr; Pt/Pd means Pt or Pd or both are present in the phase; and where the Ni is present alone or with other alloying elements, in a β (Ni, Pt)Al outer phase of the coating. For brevity the ternary or higher X—Pt/Pd—Ni phase will be termed “μ phase”. The metastable μ phase is present and observable in the early formation stages of coating development. The μ phase can be observed in as-deposited condition of the coating; e.g. in an as-CVD deposited condition of the coating, depending on parameters employed.

In an illustrative embodiment of the invention, a Pt—Al—Hf aluminide bond coating comprises a Pt concentration of about 18 atomic % across a coating thickness region straddling the Hf₂Pt₃Ni_(z) μ phase from one side to the other. The bond coating has an Al concentration of about 31 to about 40 atomic %, such as about 35 to about 40 atomic % in certain embodiments, at the same thickness region straddling the Hf₂Pt₃Ni_(x) μ phase from one side to the other. The bond coating has an Hf concentration of about 0.25 to about 1.0 atomic % across the same thickness region straddling the Hf₂Pt₃Ni_(z) μ phase from one side to the other. The overall bond coating thickness is in the range of about 25 to about 45 microns, typically about 30 to about 40 microns.

The present invention provides a Pt—Al—X bond coating where X is Hf and/or Zr that can be used beneath a TBC and improve TBC spallation life in service at elevated temperatures. In an embodiment of the invention, the Pt—Al—X aluminide bond coating includes an outer coating surface where the Pt content is about 2 to about 16 atomic %, such as about 10 to about 16 atomic % in certain embodiments, and where the Al content is about 31 to about 40 atomic %, such as about 35 to about 40 atomic % in certain embodiments, and has an overall coating thickness of about 25 to about 45 microns, such as typically about 30 to about 40 microns where the overall coating thickness includes the diffusion zone and outer additive region. This embodiment may not have the above μ phase present in the coating microstructure in the event the coating is subjected to aluminizing times/temperatures or subsequent thermal exposures causing the metastable phase to dissolve.

The present invention also provides a method comprising introducing an intermediate element (e.g. Pt and/or Pd) on or in a surface region of an alloy substrate having a low solubility for another alloying element (e.g. Hf and/or Zr) followed by introducing said another alloying element in the intermediate element (e.g. Pt and/or Pd) under deposition conditions to form a surface region of the substrate that is enriched in said intermediate element and said another element.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1( a) and 1(b) are Pd—Hf and Pt—Zr phase diagrams, respectively.

FIG. 2 is partial phase diagram information of the Hf—Pt system.

FIG. 3( a) is an SEM backscattered image of CVD Hf on Pt plated Ni base superalloy.

FIG. 3( b) shows the composition profile of CVD Hf on Pt plated Ni base superalloy.

FIG. 4( a) is an SEM backscattered image of CVD Hf plus Al on Pt plated Ni base superalloy and a corresponding composition profile of the coated surface region.

FIG. 4( b) shows the composition profile of CVD Hf and Pt only showing 20% to 30% Hf to Pt ratio.

FIG. 5 shows results from samples of experiment 3 showing the formation of the μ phase with Pt plated sample and no μ phase without Pt plating.

FIG. 6 is an SEM image of a sample of experiment 4 with higher AlCl₃ than experiment 3.

FIG. 7 contains SEM images of samples of experiments 3 and 4 before (as-coated) and after heat treatment at 2050 degrees F. for 2 hours in vacuum.

FIG. 8 is an SEM image of a sample of experiment 5 showing no evidence of the μ phase.

FIG. 9 shows spot analyses of sample of experiment 3 with substantial Hf in (Ni,Pt)Al β phase.

FIG. 10 is a Wellbull plot of baseline commercial outward type Pt—Al coating (MDC-150L) and experiment 6 variants.

FIG. 11 is a bar graph showing spallation life in cyclic oxidation testing (at 1135 C) of TBC samples having bond coats made pursuant to a method embodiment using different surface amounts of a Pt layer electroplated on the samples, No Pt layer, 2 mg/cm² Pt layer, a 4 mg/cm² Pt layer, a 6 mg/cm² Pt layer, and a 8 mg/cm² Pt layer before bond coating aluminization and hafnization. The samples are compared to similar samples that were made using 10 mg/cm² Pt layer electroplated on the samples before bond coating aluminization and hafnization. The samples also are compared to baseline TBC-coated MDC-150L samples having a 10 mg/cm² Pt layer with standard production aluminizing time and thus is representative of a commercial production coating.

DETAILED DESCRIPTION OF THE INVENTION

For purposes of illustration, the Pt—Al—X coatings where X is Hf and/or Zr will be described with respect to chemical vapor deposition (CVD) aluminide diffusion coatings where changes or modifications to conventional CVD coating parameters (U.S. Pat. No. 5,788,823) employed to form outwardly grown aluminide diffusion coatings were made as follows. The first and second changes are interelated and involve making the aluminide bond coating thinner and leaner in Al content. For example, the coating thickness can be about 30 to about 40 microns where the coating thickness includes the coating affected zone, diffusion zone and the additive region. In Al lean NiAl, the Ni diffuses about 3-5 times faster than the Al. This is the basis for the outward type aluminizing process. This phenomenon continues with additional time at temperature after the coating process is complete. In either case, the higher flux of Ni diffusing outward causes the NiAl to swell and generates a diffusion related strain that contributes to the rumpling phenomenon observed on many aluminide coatings. (The biggest strain contribution to rumpling is from the coefficient of thermal expansion mis-match between the γ/γ′ alloy and the β NiAl. But the swelling phenomenon also contributes.) The higher the Al content, the more Ni is needed from the substrate to reach the steady state Al content of 30-32 atomic % and the more swelling of the NiAl. A thinner and leaner Al content bond coating will require less Ni diffusion from the alloy during formation of the coating and during high temperature service exposure. Starting with a thinner, lower Al content coating according to the invention, will allow the coating system to reach 30-32% Al concentration (the steady state Al content with gamma prime (γ′)) with less Ni transport and less strain to contribute to the rumpling phenomenon that leads to early TBC spallation.

The third change is a higher surface Pt content in the bond coating of the invention. Again, coating time can alter this. The Pt is plated onto the alloy substrate surface prior to aluminization as described in U.S. Pat. No. 5,788,823. Pt is substitutional with Ni in the γ, γ′ and β phases of the Ni—Al system. The Pt distribution in commercial production MDC-150L coating is bell shaped with about ½ of the Pt diffusing with Ni to form the additive layer of the coating and about ½ diffusing into the diffusion zone toward the alloy.

When plated with 10 mg/cm² Pt, commercial production coating times produce a coating outer surface Pt content in the range of 4-8 atomic %. By coating for short times (e.g. 540 minutes or less) pursuant to the invention, the thinner coating of the invention results in higher Pt content at the outer surface of the bond coating. For best TBC spallation results (i.e. prolongation of spallation life of TBC), the Pt content at the outer surface of the bond coating of the invention is in the range of about 10 to about 16 atomic %, which is higher due to less time (e.g. 210 minutes or less coating time) for Pt to be diluted by Ni diffusion from the substrate. Additionally, more Pt content can be provided at the outer surface if desired by plating a greater amount of Pt on the substrate before CVD aluminizing.

Lastly, co-deposition or sequential deposition of Hf (and/or Zr) with the Al to form the coating allows for Hf (and/or Zr) to become incorporated into the β (Ni,Pt)Al outer coating phase. Various explanations of the beneficial effects of reactive elements (Hf, Y, La, Ce, Er) on Ni based material oxidation have been reported in addition to the effect Hf has on TBC spallation life. But the addition to β (Ni,Pt)Al phase at significant levels is also difficult to achieve in a CVD, Above the Pack, or a pack coating environment. Consequently, an embodiment of this invention is a modified CVD process that produces substantial Hf (and/or Zr) incorporation into the β (Ni,Pt)Al outer coating phase via the formation of an Hf₂Pt₃Ni_(z) metastable (transition) μ phase. In this case Ni_(z) is nickel plus possible other elements in the alloy system to provide ternary, quaternary or higher alloys present in the β (Ni,Pt)Al phase. For example, for Ni_(z), z can be 5 when only Ni is present and is less than 5 when the metastable phase includes other alloying elements present in the alloy system in the β (Ni,Pt)Al coating phase (e.g. Ni_(5-z) where z is/are other alloying elements in atomic % present in the phase). When Pd plating is used in lieu of Pt plating, another embodiment provides a modified CVD process that produces substantial Hf (and/or Zr) incorporation into the β (Ni,Pd)Al coating phase via the formation of an HfPdNi_(z) metastable ternary or higher μ phase where z can be 4 when only Ni is present and is less than 4 when the ternary or higher phase includes other alloying elements present in the alloy system in the β (Ni,Pd)Al coating phase (e.g. Ni_(4-y) where y is/are other alloying elements in atomic % present in the phase).

One embodiment of the Pt—Al—X bond coats pursuant to the invention are unique in that the bond coat includes an outer coating surface where the Pt content is about 2 to about 16 atomic %, preferably about 10 to about 16 atomic %, and where the Al content is about 31 to about 40 atomic %, preferably about 35 to about 40 atomic % and has a coating overall thickness of about 25 to about 45 microns, typically about 30 to about 40 microns, where the coating overall thickness includes the coating affected zone, diffusion zone and additive β (Ni,Pt)Al region. This embodiment may not have the above μ phase present in the coating microstructure in the event the coating is subjected to subsequent the longer alumizing cycles, e.g. greater than 120 minutes, or post aluminizing thermal exposures causing the metastable phase to dissolve.

Another embodiment of the Pt—Al—X bond coats pursuant to the invention is unique in that the bond coat includes the μ phase in the mid-region of the coating (e.g. within the middle 40 to 60% of the as-deposited coating thickness) that is thought to be the position of the Pt plating prior to CVD aluminizing/hafnizing. The presence of the Pt is critical for Hf/Zr uptake from the CVD coating gas environment and the ability of the β (Ni,Pt)Al phase to hold significant levels of Hf and/or Zr in solid solution. The bond coat pursuant to the invention is capable of increasing the TBC spallation life at least 2× (two times) and potentially 3× longer than the commercial production MDC-150L coating (see U.S. Pat. No. 5,788,823). This invention can be practiced using the same basic processing equipment as the commercial production MDC-150L coating (U.S. Pat. No. 6,793,966 without gas inlet preheater 52) for purposes of illustration and not limitation. Practice of a method embodiment of the invention that involves depositing the Hf before the Al to charge the Pt-rich surface with Hf before Al deposition may improve uniformity of Hf deposition and allow use of other coating gas distribution conduits in practice of the invention. Moreover, another method embodiment of the invention envisions using a CVD Hf coating gas generator and setting of the coat temperature below the above-the-pack activator reaction temperature to charge the Pt rich surface with Hf, and then raising the coat temperature to above the activator reaction temperature to start aluminizing.

Examination of a series of phase diagrams provides insight into the concept of this invention. FIGS. 1( a) and 1(b) show published phase diagrams of the Pd—Hf and Pt—Zr binary alloy systems {Ref: Binary Alloy Phase Diagram 2^(nd) Edition, ASM International, 1990}. FIG. 2 shows published information of the Pt—Hf binary alloy system. By virtue of their location on the Periodic Table of Elements, Pd is above Pt and Zr is above Hf in their respective columns, these respective element pairs have similar properties. FIG. 1( a) shows that at 1080 C (degrees C.), Pd can hold more than 20 at. % of Hf in solid solution. Similarly, FIG. 1( b) shows that Pt can hold more than 20 at. % Zr in solid solution. Limited data on Pt—Hf suggested that Pt could hold up to 10 at. % in solid solution with the existence of an HfPt₄ phase. The FIG. 1 diagrams do not show an HfPd₄ or HfZr₄ phase. Consequently there is not complete agreement between the phase stability information as to the maximum solid solution solubility of Hf in Pt. Nonetheless, the data suggest that there is at least 10 at. % solid solution solubility which is more than enough to provide Hf/Zr doping of the bond coat surface in preparation for bond coat formation and TBC application. Hf doping to the 0.05% to 1% in (Ni,Pt)Al bond coats can be sufficient to improve TBC spallation life.

The invention uses the high Hf/Zr solubility in Pt to charge the alloy surface (substrate) with Hf/Zr. By Pt plating the Ni based alloy substrate, the substrate surface is very rich in Pt and provides the opportunity for Hf/Zr to be introduced into the Pt rich surface at high dopant levels. To prove this point, a Chemical Vapor Deposition experiment was conducted that utilized only HfCl₄ coating gas.

The experiment applied 10 mg/cm² Pt (U.S. Pat. No. 5,788,823) to the surface of a commercially available single crystal Ni-based superalloy (CMSX-4®) 1-inch diameter×0.125 inch thick coupons. The coupons were suspended in a CVD reactor (similar to that of U.S. Pat. No. 6,793,966 without gas inlet preheater 52). The CVD reactor was thermally ramped to 1080 C under a gas mixture of H₂/12.7 volume % Ar at 200 torr. During the thermal ramp, the Pt plate and the Ni superalloy begin to interdiffuse. Once the reactor is at 1080 C, HCl gas is fed into the Hf generator (U.S. Pat. Nos. 6,291,014; 6,793,966; and 6,689,422) to create a coating gas mixture of H₂/12.6 volume % Ar/0.14 volume % HfCl₄ in the coating retort. The Hf deposition portion of the coating cycle was held constant for 25 minutes. Then the retort was cooled and the samples removed for examination.

FIG. 3 a shows a scanning electron microscope back scatter image and FIG. 3 b shows the composition profile of the resultant coating. The formation of a high atomic number rich layer is clear by the strong brightness of the near surface. The composition profile, FIG. 3( b) confirms that the surface is enriched in Hf and the Hf₂Pt₃Ni_(z) μ phase is present prior to any aluminization processing. In this case Ni_(z) is nickel plus possible other substrate elements. In this case, other substrate elements in the μ phase are Co, Ta, Cr, and Al. When combined, the other substrate elements comprised about 6.5 atomic % of the phase.

A second experiment was performed using the same process as described above except the Hf only portion was increased to 45 minutes and the HfCl₄ was increased to 0.16 volume % and the Ar to 15.0 volume % and also the AlCl₃ portion was added after the 45 minutes. The combined HfCl₄ and AlCl₃ gas mixture flowed for 165 more minutes for a total coating cycle of 210 minutes. The combined coating gas mixture comprised H₂/13.6 volume % Ar/0.15 volume % HfCl₄, and 0.8 volume % AlCl₃. FIGS. 4 a and 4 b show the coating and Hf and Pt composition profile made from this process. With the additional formation of the additive layer of the outward type diffusion aluminide processing, the β (Ni,Pt)Al coating phase has formed over the μ phase. Ni and Pt must be able to transport through the μ phase and react with the AlCl₃ to form the β phase. Also the μ phase has changed shape. The irregular outer surface of the μ phase (adjacent the Ni plating) in FIG. 3 a is smooth in FIG. 4 a. The smooth inner surface of μ phase in FIG. 3 a is irregular in FIG. 4 a. The continuous μ phase in FIG. 3 a has gaps in FIG. 4 a. These changes suggest that Ni, Pt, and Hf from the FIG. 3 a μ phase are diffusing. The outer surface is dissolving and becoming smooth as the additive layer forms. The inner surface is growing towards the diffusion zone in an irregular fashion. If the local chemical conditions are correct, the μ phase dissolves to form the gaps.

Experiments three and four were performed using the same process as experiment 2 except the Hf and Al coating gases were activated at the same time once the retort was at 1080 C and the coating gas was changed to H₂/12.6 vol. % Ar/0.2 vol. % AlCl₃/0.14 vol. % HfCl₄ for experiment 3 and H₂/12.6 vol. % Ar/0.4 vol. % AlCl₃/0.14 vol. % HfCl₄ for experiment 4. The total coating time remained at 210 minutes for both experiments. In addition to the Pt plated coupons, non-Pt plated coupons were also added to experiment 4 to understand the criticality of Pt at the surface in such a process. FIGS. 5 and 6 show the coatings resulting from these processing. The Pt plated samples have similar characteristics to experiment 2 while the non-Pt plated sample has no μ phase.

A general trend is also noted in that, as the AlCl₃ content of the coating gas is increased, less of the μ phase is observed. In experiment 2, initially there is only Hf available and the μ phase is readily visible in the microstructure. As Al availability increases in experiments 3 and 4, it competes with Hf for reaction with the Pt modified surface and less μ phase is observed.

Remnant samples from experiments 3 and 4 were heat treated at 2050 F (degrees F.) for 2 hours in a vacuum. FIG. 7 illustrates how the initial μ phase is altered by this heat treatment showing that the μ phase is metastable and will dissolve with time at temperature. The bright μ phase of experiment 3 is diminished to a ghost image of a lesser amount of μ phase after heat treatment. The minimal amount of μ phase in the experiment 4 sample is completely dissolved.

A fifth experiment to show the metastable nature of the μ phase was conducted using the same parameters as experiment 4 except the AlCl₃ was increased to 0.8 vol. % and the coating time was extended to 420 minutes. As shown in FIG. 8, the higher coating gas AlCl₃ content and longer coating time reduce the amount the μ phase to the point it is not distinguishable.

An objective of the invention is to provide a method to add Hf (and/or Zr) to the (Ni,Pt)—Al bond coat. In particular, Hf enrichment of the additive layer of the bond coat that forms the thermally grown oxide to which the thermal barrier coating is anchored. Work with ternary Ni—Al—Hf systems suggests that there is very low solubility for Hf in the Ni—Al β phase. However, the coating formed on a Ni superalloy forms with other elements from the superalloy allowing for subtle solubility changes. Additionally, Al lean, β-NiAl is a more defected crystal structure allowing for higher solubility of other elements. FIG. 9 shows a set of spot analyses of a sample made in experiment 3. The spots are divided into 3 groups. The outboard spots are in the β (Ni,Pt)Al coating regions above the μ phase and the inboard spots are in the β (Ni,Pt)Al coating regions below the μ phase. The Hf content of the inboard and outboard β (Ni,Pt)Al coating regions ranges between about 0.5 and about 1.0 atomic %.

With the above ability to charge up the Pt rich surface with Hf via the μ phase, the ultimate benefit of this invention is to improve the spallation life of the TBC. To demonstrate this, a baseline coating process (MDC-150L) and three versions of experiment 6 produced 156 bond coated spallation test coupons. The three versions of experiment 6 used the same coating cycle parameters of experiment 5 except for coating gas time. Experiment 6A used 120 minutes, 6B used 210 minutes, and 6C used 420 minutes, the same as experiment 5. To show the importance of Pt plating for Hf charging, Experiments 6A, 6B, and 6C had 4 coupons with no Pt plating. To minimize test biasing from the TBC deposition processing, the coupons were TBC coated in a series of runs with coupons from all four bond coat processes in each of the TBC coating cycles. The TBC (thermal barrier coating) comprising yttria-stabilized zirconia was applied following the process described in U.S. Pat. No. 5,716,720.

Table 3 set forth below is a summary of experimental processing parameters for the 6 experiments (exp.).

Cyclic Testing was performed in vertically mounted Lindberg Tube Furnaces with a suspended sample tree that drops the samples into the furnace for the exposure time and then elevates them to cool to near room temperature. The test cycle is 50 minutes in the furnace and 10 minutes of cooling. The test temperature is 2075 degrees F. Each Test Rig has automated controllers for conducting the testing around the clock. Before the start of the tests and at furnace service times, the furnace is surveyed to 2075 degrees F.±10 F.

Each test is run for 20 cycles and allowed to cool before resetting the counter for an additional 20 cycles. During the 4 hour hold period, the samples are inspected for failure. After 100 cycles, the samples are removed from the test rigs and held for the 4 hour holding period and inspected for failure. In each case, failure is defined as 20% of the face of the coupon having TBC spallation.

There are 4 Test Rigs with the above description. Each sample tree holds 40 coupons. Since only 40 can be tested at once, additional coupons are added as failed coupons are removed from the test.

FIG. 10 shows results of the TBC spallation testing of the four bond coats. The graph is a Weibull plot were the y-axis is a Cumulative % Failure following the formula: Failure=(R−0.3)/(N+0.4)*100

-   -   R=Failure Rank (1, 2, 3, 4, . . . )     -   N=Total Number of Failures

The x-axis is the cyclic spallation cycles at failure for the corresponding rank of failure.

Each data set has a Characteristic Life, which is the Cumulative % Failure at 63.2%, and a shape parameter, which is the slope of the data set. For TBC spallation life, extending Characteristic Life and/or increasing the slope are desirable qualities.

From FIG. 10 and Table 2 set forth below, it is clear that all 3 versions of Experiment 6 show a substantial improvement over the commercial production MDC-150L baseline (901 cycles). The longer time Experiment 6C showed the least improvement with a characteristic life of 2035 cycles while the shorter time Experiments 6A and 6B showed characteristic lives of 2643 and 2674 respectively. The slopes of the Experiment 6 versions are not as steep as the MDC-150L baseline with the longer 6C Experiment having the poorest slope. The effect of bond coating time on TBC spallation life is perhaps explained by the loss of Hf due to more diffusion of Hf into the superalloy and away from the TBC/TGO interface, although applicant does not wish or intend to be bound by any theory or explanation in this regard. There appears to be an optimal coating time to achieve maximum TBC spallation life.

Table 2 includes data from Experiments 6A, 6B, and 6C where the Pt plating was not applied to a subset of the samples. This data clearly shows that these samples performed below the baseline MDC-150L characteristic life reinforcing the need for a Pt rich surface to dissolve and retain Hf in the bond coat.

The above examples show how manipulation of CVD processing parameters can affect the concentration and distribution of Hf in the bond coatings and hence TBC spallation life. The CVD process methodology gives extra degrees of freedom versus pack or above-the-pack coating processing where all constituents must be introduced into the coating environment as the same time. CVD processing allows for control of when and for how long each gas species is present in the coating environment. The above experiments represent a sampling of these possibilities and do not restrict the invention to only those mentioned.

Another embodiment of the present invention involves forming the bond coating as described above yet using a lesser amount of the applied Pt (or Pd) electroplated layer before aluminization. For example, the above embodiments of the invention employed an initial Pt electroplated layer having 10 mg/cm² Pt on the sample surface. The following examples employ various lesser amounts of the Pt layer; namely, no Pt, 2 mg/cm² Pt layer, 4 mg/cm² Pt layer, 6 mg/cm² Pt layer, and 8 mg/cm² Pt. These samples plus the earlier standard of 10 mg/cm² were then aluminized according to Experiment 6B described above to form the bond coat on the Pt plated substrate.

Referring to FIG. 11, a bar graph is provided showing spallation life in cyclic oxidation testing (1135 C) of TBC samples (as described above) having bond coats made using the different surface amounts of the Pt layer electroplated on the samples before bond coating (aluminization+hafnization). The samples designated 0 Pt, 2 Pt, 4 Pt, 6 Pt and 8 Pt are compared to similar samples designated 10 Pt and 10 Pt MDC-150L, The grey bars were bond coated using the Exp. 6B parameters (aluminization+hafnization) while the black bars, baseline MDC-150L, coating was aluminized per the production practice. Note that 3 samples had not failed at this point in the testing.

FIG. 11 reveals that as the amount of the Pt electroplated layer on the sample surface is increased from 0 mg/cm² Pt to 10 mg/cm² Pt, the spallation life is substantially improved, on average, as compared to average spallation life of the baseline TBC-coated MDC-150L samples. Moreover, FIG. 11 reveals that a lesser amount of the Pt electroplated layer can be used and still provide a spallation life that is equivalent or better than the spallation life provided by the TBC-coated MDC-150L samples representative of a commercial production coating. This embodiment permits a reduction in the amount of Pt (or Pd) used as a result of the presence of Hf and/or Zr in the coating in effective amount to achieve oxidation resistance substantially equivalent to that of MDC-150L commercial coating. This embodiment with reduced Pt layer amounts can be employed in making of the bond coat and thus achieve substantial reduction in materials cost to make the bond coat wherein the bond coat will provide TBC spallation life in cyclic oxidation testing as good as or better than that of MDC-150L commercial coating.

TABLE 2 Pt Characteristic Bond Coat (gm/cms²) Life Slope MDC-150L 10 901 10.2 Exp 6A 10 2643 6.2 ″ 0 455 3.0 Exp. 6B 10 2674 6.5 ″ 0 393 5.1 Exp 6C 10 2035 3.0 ″ 0 358 10.2

TABLE 3 Coating Retort Gas Volume Percent Exp. Cycle Time H2 AlCl3 HfCl4 Ar 1 2690 25 85 0 0.17 15.2 2 2335 Hf 45 85 0 0.16 14.9 ″ 2335 Al + Hf 165 85 0.9 0.15 13.6 3 2209 210 87 0.2 0.14 12.6 4 2229 210 87 0.4 0.14 12.6 5 2414 420 86 0.8 0.14 12.6 6A 2399 120 86 0.8 0.14 12.6 6B 2402 210 86 0.8 0.14 12.6 6C 2414 420 86 0.8 0.14 12.6

Although the present invention has been described with respect to certain illustrative embodiments, those skilled in the art will appreciate that modifications and changes can be made therein within the scope of the invention as set forth in the appended claims. 

The invention claimed is:
 1. A method of making a diffusion aluminide coating on a Ni based substrate, comprising providing at least one of Pt and Pd at a surface region of the substrate to provide an enriched surface region which is enriched in at least one of Pt and Pd, depositing by chemical vapor deposition at least one of Hf and Zr on said enriched surface region using such coating gas composition comprising at least one of Hf-bearing coating gas and Zr-bearing coating gas in an amount that a reaction of Hf and/or Zr with said enriched surface region forms a metastable non-aluminide phase layer before the diffusion aluminide coating is formed wherein the non-aluminide phase layer comprises an intermetallic phase comprising at least one of Pt and Pd, at least one of Hf and Zr, and Ni different from a β nickel aluminide phase of the diffusion aluminide coating to be formed, wherein said metastable phase layer is not enriched in Al as compared to the substrate and to the diffusion aluminide coating to be formed, and aluminizing the non-aluminide phase layer to form the diffusion aluminide coating on the non-aluminide phase layer and to form an inner diffusion aluminide zone in the substrate beneath the non-aluminide phase layer such that the non-aluminide phase layer resides as a metallographically distinct layer between the diffusion aluminide coating and the inner diffusion aluminide zone, wherein the diffusion aluminide coating is formed to have a β nickel aluminide phase enriched through its thickness in at least one of Pt and Pd and at least one of Hf and Zr as it is formed on the non-aluminide phase layer, which has a higher content of at least one of Pt and Pd and at least one of Hf and Zr than the β nickel aluminide phase.
 2. The method of claim 1 wherein Pt is deposited on the surface region in an amount from about 2 mg/cm² to about 10 mg/cm² Pt or more.
 3. The method of claim 2 wherein Pt is deposited on the surface region in an amount from about 4 mg/cm² to about 10 mg/cm² Pt.
 4. The method of claim 1 including discontinuing aluminizing to retain the non-aluminide phase layer in a microstructure of the coating.
 5. The method of claim 1 including continuing aluminizing until the non-aluminide phase layer is dissolved into the β nickel aluminide phase of a microstructure of the coating.
 6. The method of claim 1 wherein said at least one of Hf and Zr is/are codeposited with aluminum on the enriched surface region.
 7. The method of claim 1 wherein said at least one of Hf and Zr is/are deposited on the enriched surface region followed by deposition of aluminum.
 8. The method of claim 1 wherein the non-aluminide phase layer comprises Hf and/or Zr, Pt, and Ni or Hf and/or Zr, Pd, and Ni when the substrate is a nickel alloy.
 9. The method of claim 1 wherein there is a maximum content of said at least one of Hf and Zr between the diffusion aluminide coating and the inner diffusion aluminide zone.
 10. The method of claim 1 wherein the coating gas composition includes a content of a coating gas bearing at least one of Hf and Zr and a content of a coating gas bearing Al effective to form the non-aluminide phase layer before forming the diffusion aluminide coating on the non-aluminide phase layer.
 11. A method of forming an outer diffusion aluminide coating on a nickel-containing substrate, comprising: a) providing at least one of Pt and Pd at a surface region of the substrate having a low solubility for at least one of Hf and Zr wherein the surface region is enriched in at least one of Pt and Pd, b) depositing at least one of Hf and Zr by chemical vapor deposition on the surface region using such a coating gas composition comprising at least one of Hf-bearing coating gas and Zr-bearing coating gas in an amount that a reaction of Hf and/or Zr with the surface region forms a non-aluminide phase layer comprising Pt/Pd, Hf/Zr and Ni before the outer diffusion aluminide coating is formed, wherein Pt/Pd is Pt or Pd or both Pt and Pd and Hf/Zr is Hf or Zr or both Hf and Zr, and c) forming the outer diffusion aluminide coating on said non-aluminide phase layer such that said non-aluminide phase layer resides as a metallographically distinct layer adjacent said outer diffusion aluminide coating between said outer diffusion alumsinide coating and a diffusion aluminide zone in the substrate.
 12. The method of claim 11 wherein said phase layer comprises about 20 atomic % Hf, about 30 atomic % Pt, about 2.5 to about 4.4 atomic % Al and balance essentially Ni and other substrate elements.
 13. The method of claim 11 including continuing to form the outer diffusion aluminide coating at least until the non-aluminide phase layer dissolves into the outer diffusion aluminide coating.
 14. The method of claim 11 including chemical vapor depositing Hf/Zr and Al sequentially or concurrently.
 15. A method of forming a diffusion aluminide coating on a nickel-containing substrate, comprising: a) providing Pt at a surface region of the substrate to provide a Pt-enriched surface region, b) depositing Hf by chemical vapor deposition on the Pt-enriched surface region using such a coating gas composition containing a Hf-bearing coating gas and an Al-bearing coating gas in amounts that a reaction of Hf with said Pt-enriched surface region forms a non-aluminide phase layer comprising Hf, Pt, and Ni before the diffusion aluminide coating is formed, and c) forming the diffusion aluminide coating on said non-aluminide phase layer such that said non-aluminide phase layer is adjacent said diffusion aluminide coating between said diffusion aluminide coating and a diffusion aluminide zone in the substrate.
 16. The method of claim 15 wherein said non-aluminide phase layer comprises about 20 atomic % Hf, about 30 atomic % Pt, about 2.5 to about 4.4 atomic % Al, and balance essentially Ni and other substrate elements. 